Method for producing hydrosilanes containing carbon

ABSTRACT

The present invention provides processes for preparing carbon-containing hydridosilanes, in which an optionally boron- or phosphorus-doped hydridosilane is reacted without catalyst and reducing agent with at least one carbon source selected from linear, branched or cyclic carbosilanes, halogenated hydrocarbons, carbenes, alkyl azides, diazomethane, dimethyl sulphate or alcohols, the carbon-containing hydridosilane oligomers obtainable by the process and the use thereof.

The present invention relates to a process for preparingcarbon-containing hydridosilanes, to the carbon-containinghydridosilanes themselves and to the use thereof.

Hydridosilanes and mixtures thereof are described in the literature aspossible reactants for the production of silicon layers, which find usein the semiconductor industry inter alia. Hydridosilanes are understoodto mean compounds which contain essentially only silicon and hydrogenatoms. Hydridosilanes may be gaseous, liquid or solid and are—in thecase of solids—essentially soluble in solvents such as toluene orcyclohexane or in liquid silanes such as cyclopentasilane. Examplesinclude monosilane, disilane, trisilane, cyclopentasilane andneopentasilane. Hydridosilanes having at least three or four siliconatoms may have a linear, branched or (optionally bi-/poly-)cyclicstructure having Si-H bonds, and can be described by the respectivegeneric formulae Si_(n)H_(2n+2) (linear or branched; where n ≧2),Si_(n)H₂ (cyclic; where n≧3) or Si_(n)H_(2(n−i)) (bi- or polycyclic;n≧4; i={number of cycles}−1).

It is possible in principle to produce silicon layers via variousprocesses. Among these, however, sputtering techniques have thedisadvantage that they have to be performed under high vacuum. Gas phasedeposition processes, for example CVD or PVD, have the furtherdisadvantage that they require i) the use of very high temperatures inthe case of a thermal reaction regime or ii) high energy densities inthe case of introduction of the energy required for the decomposition ofthe precursor in the form of electromagnetic radiation. In both cases,it is possible only with a very high level of apparatus complexity tointroduce the energy required to decompose the precursor in a controlledand homogeneous manner. Since the other processes for production ofsilicon layers are also disadvantageous, silicon layers are thuspreferably formed via depositions from the liquid phase.

In such liquid phase processes for production of silicon layers, liquidreactants (optionally functioning as solvents for further additivesand/or dopants) or liquid solutions containing the reactants (which arethemselves liquid or solid) (and optionally further additives and/ordopants) are applied to the substrate to be coated and subsequentlyconverted thermally and/or with electromagnetic radiation to a siliconlayer. For example, US 2008/0022897 A1 discloseshydridosilane-containing coating compositions including dopants forproduction of thin semiconductor films.

Even though it is possible in principle to use many hydridosilanes forthe silicon layer production, it has been found that only higherhydridosilanes, i.e. hydridosilanes having at least 10 silicon atoms, orsolutions thereof give good coverage of the surface of customarysubstrates in the course of coating thereof and can lead to homogeneouslayers with few defects. For this reason, processes for preparing higherhydridosilanes are of interest. Many higher hydridosilanes can beprepared by oligomerization of lower hydridosilanes. In the case of suchan oligomerization of lower hydridosilanes viewed in a formal sense, onehydridosilane molecule of higher molecular weight is formed from two ormore lower hydridosilane molecules after abstraction of hydrogen and/orrelatively small hydridosilyl radicals.

However, silicon layers produced from pure hydridosilanes often still donot have satisfactory properties for semiconductor applications,especially for optoelectronic applications. Thus, it would be desirableto be able to produce silicon-based layers with greater optical bandgaps(which are suitable in principle to absorb radiation over a widewavelength range in solar cells, i.e. constitute a “wide bandgap”material). It would also be desirable to produce silicon-based layerswith a particularly small refractive index which enable better opticalinjection of the radiation. In addition, it would be desirable to beable to produce silicon-based layers with particularly good opticaltransmission.

U.S. Pat. No. 5,866,471 A discloses processes for producing thinsemiconductor layers, in which not only solutions of hydridosilanes butalso solutions comprising alkylated hydridosilanes are used. Generalprocesses for preparation of the alkylated hydridosilanes are notdescribed. In the examples, a process for preparing alkylatedhydridosilanes is disclosed, in which metallic sodium is used. However,this has the disadvantage that salts formed have to be removed in acostly and inconvenient manner, and disadvantageous metallated silanecompounds can form as a by-product.

U.S. Pat. No. 6,020,447 A discloses a process for preparing alkylatedhydridosilanes, in which a polysilane precursor is reacted with areducing agent, preferably sodium, potassium, lithium and alloysthereof. Here too, disadvantageous ionic by-products are formed, and thereducing agent has to be removed in a costly and inconvenient manner.

U.S. Pat. No. 5,700,400 A discloses, in the context of a process forproducing a semiconductive material, an intermediate of adehydrogenating condensation of optionally alkylated mono-, di- ortrisilane. However, the condensation is effected with addition of acatalyst selected from a metal or a metal compound of particular groupsof the periodic table. These catalysts, however, have disadvantages.More particularly, it is disadvantageous that the removal thereof fromthe reaction mixture is very costly and inconvenient when particularlypure silicon layers are to be produced.

With respect to the outlined prior art, the problem addressed is thusthat of providing a process for preparing carbon-containinghydridosilanes, which avoids the disadvantages of the prior art. Moreparticularly, the problem addressed by the present invention is that ofproviding a process for preparing carbon-containing hydridosilanes, inwhich there is no need to remove reducing agents or catalysts in acostly and inconvenient manner, and in which no disadvantageousby-products form.

The problem which is thus addressed is solved in accordance with theinvention by a process for preparing carbon-containing hydridosilanes,in which

-   -   an optionally boron- or phosphorus-doped hydridosilane is        reacted    -   without catalyst and reducing agent    -   with at least one carbon source selected from        -   linear or branched carbosilanes of the generic formula            Si_(b)H_(2b+2−y)R_(y) where b ≧2, 1≦y ≦2b+2 and            R=—C₁-C₁₀-alkyl, —C₆-C₁₀-aryl, -C₇-C₁₄-aralkyl,        -   cyclic carbosilanes of the generic formula            Si_(c)H_(2c−y)R_(y) where c ≧3, 1y≦2c and R=—C₂-C₁₀-alkyl,            —C₆-C₁₀-aryl, —C₇-C₁₄-aralkyl,        -   halogenated hydrocarbons of the generic formula            C_(n)H_(2n+2−y)X_(y) where 1≦n ≦5, 1≦y ≦12 and X=F, Cl, Br,            I,        -   carbenes of the generic formula CRR′ with R, R′=—H, —F, —Br,            —I, —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,            —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,            —C₂-C₁₀-heteroalkenyl, —C₅-C₁₀-heteroaryl, —C₇-C₁₄-aralkyl,            —OR″ where R″=—C₁-C₁₀-alkyl, —C₂-C₁₀-(cyclo)alkenyl,            —C₆-C₁₀-aryl, —NR′″₂ where R′″=—C₁-C₁₀-alkyl,            —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —Si_(n)R^(Iv) _(n+1)            where R^(IV)=—H, —C₁-C₁₀-(cyclo)alkyl,            —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —(CO)-R^(V) where            R^(V)=—H, —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,            —C₆-C₁₀-aryl, —CO)—OR^(vi) where W^(vi)=—H,            —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆ ⁻C₁₀-aryl,            —CN, —NC, —SR^(Vii) where R^(Vii) =—H, —C₁-C₁₀-(cyclo)alkyl,            —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —S(O)₂R^(viii) where            R^(viii)=—H, —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,            —C₆C₁₀-aryl, —P(R^(ix))₂ where R^(ix)=—H,            —C₁—C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl,            or where R and R′ together represent a bidentate bridging            radical selected from =C₃-C₂₀-(cyclo)alkyl,            =C₃-C₂₀-(cyclo)alkenyl, =C₃-C₂₀-(cyclo)heteroalkyl, =C₃-C₂₀            heteroalkenyl and =C₆-C₁₄-(hetero)aralkyl,    -   carbene analogues, especially CO and CN⁻,    -   alkyl azides of the generic formula N₃R^(x) where        R^(x)=—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,        —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,        —C₂-C₁₀-(cyclo)heteroalkenyl, —C₅-C₁₀-heteroaryl,        —C₇-C₁₄-aralkyl,    -   diazomethane H₂CN₂,    -   dimethyl sulphate C₂H₆O₄S,    -   or alcohols of the generic formula HOR^(xi) where        R^(xi)=—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,        —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,        —C₂-C₁₀-(cyclo)heteroalkenyl, —O₅-C₁₀-heteroaryl,        —C₇-C₁₄-aralkyl.

The hydridosilanes to be used as the reactant are compounds containingessentially only silicon and hydrogen atoms. They may include dopantatoms in a low proportion, especially boron or phosphorus.Hydridosilanes usable with preference satisfy the generic formulaSi_(n){BH}_(x){PH}_(y)H_(2n+2) where n=3-10, x=0 or 1 and y=0 or 1, withthe proviso that at least one of the parameters x and y=0. Thesecompounds are optionally boron- or phosphorus-doped hydridosilanes whichmay be linear or branched. Hydridosilanes of particularly goodsuitability are those of the generic formula Si_(n){BH}_(x)H_(2n+2)where n=3-10, x=0 or 1. The process according to the invention can beperformed very particularly efficiently with hydridosilanes of thegeneric formula Si_(n)H_(2n+2) where n=3-10. Corresponding compounds arelinear or branched hydridosilanes. Very particular preference is givento the hydridosilanes SiH(SiH₃)₃, Si(SiH₃)₄ and Si(SiH₃)₃(SiH₂SiH₃).

The oligomerization of the hydridosilanes in the presence of the carbonsource forms carbon-containing hydridosilane oligomers of highermolecular weight compared to the hydridosilanes used. Because of thebonds which are broken and the subsequent recombination of thehydridosilanes used and optionally also of the carbon sources in thesynthesis, these have a branched structure.

The process according to the invention additionally has the advantagethat oligomers having a particularly homogeneous distribution of thecarbon and silicon atoms, as a result of which these can also be used toproduce silicon-containing layers with a particularly homogeneousdistribution of these atoms. In addition, the process according to theinvention has the advantage that even low carbon concentrations in theoligomer can be established efficiently.

The process according to the invention is performed without catalyst andreducing agent, meaning that it is performed without the presence ofreducing agents (more particularly without the presence of elementalalkali metals or alkaline earth metals) and without the presence ofcompounds that would catalyse the oligomerization to give thecarbon-containing hydridosilane (more particularly without the presenceof transition metals, lanthanides, transition metal compounds orlanthanide compounds).

The process according to the invention is performed with at least onecarbon source. Thus, the optionally boron- or phosphorus-dopedhydridosilane can be reacted with one or more carbon sources.Preferably, because this leads to particularly good carbon-containinghydridosilanes, the process according to the invention is performed insuch a way that the optionally boron- or phosphorus-doped hydridosilaneis reacted with a carbon source. The carbon sources are selected fromthe following particular carbon sources elucidated in detailhereinafter: linear, branched and cyclic carbosilanes, halogenatedhydrocarbons, carbenes, alkyl azides, alcohols, and the compoundsdiazomethane and dimethyl sulphate. How these compounds can be preparedis known to those skilled in the art.

The carbon sources used may be linear or branched carbosilanes of thegeneric formula Si_(b)H_(2b+2−y)R_(y) where b ≧2, 1≦y≦2b+2R=C₁-C₁₀-alkyl, C₆-C₁₀-aryl, C₇-C₁₄-aralkyl, “C₁-C₁₀-Alkyl” radicals areunderstood here and hereinafter to mean radicals having 1 to 10 carbonatoms. Correspondingly, “C₆-C₁₀-aryl” radicals have 6 to 10 carbonatoms, and “C₇-C₁₄-aralkyl” radicals 7 to 14 carbon atoms. A prefix“C_(x)-C_(y)” here and hereinafter thus always denotes the minimum valuex and the maximum value y for the carbons for the preferred radicaldesignated more specifically thereafter. All alkyl radicals may belinear or else branched. In addition, all alkyl, aryl and aralkylradicals may bear substituents. More particularly, all alkyl, aryl andaralkyl radicals may be halogenated. The linear or branched carbosilanesusable as the carbon source may have exclusively carbon-containingradicals (and thus be “pure” carbosilanes) or, in addition to these, mayalso have hydrogen atoms bonded directly to silicon (and thus behydridocarbosilanes). Preference is given to linear or branchedhydridocarbosilanes of the generic formula Si_(b)H_(2b+2−y)R_(y) whereb=2-20, y=1 to 2b+1 and R=C₁-C₁₀-alkyl, C₆-C₁₀-aryl, C₇-C₁₄-aralkyl,with which a higher reactivity arises compared to “pure” linear orbranched carbosilanes, and with which, in addition, a more homogeneousdistribution of the carbon in the oligomer can also be achieved.

The carbon sources used may also be cyclic carbosilanes of the genericformula Si_(c)H_(2c−y)R_(y) where c≧3, 1≦y≦2c and R=C₂-C₁₀-alkyl,C₆-C₁₀-aryl, C₇-C₁₄-aralkyl. All alkyl radicals may be linear or elsebranched. In addition, all alkyl, aryl and aralkyl radicals may bearsubstituents. More particularly, all alkyl, aryl and aralkyl radicalsmay be halogenated. The cyclic carbosilanes usable as the carbon sourcemay have exclusively carbon-containing radicals (and thus be “pure”carbosilanes) or, in addition to these, may also have hydrogen atomsbonded directly to silicon (and thus be hydridocarbosilanes). Preferenceis given to cyclic hydrogen-containing carbosilanes of the genericformula Si_(c)H_(2c−y)R_(y) where c=3-20, y=1-(2c-1) and R=C₂-C₁₀-alkyl,C₆-C₁₀-aryl, C₇-C₁₄-aralkyl, with which a higher reactivity arisescompared to “pure” cyclic carbosilanes and with which a more homogeneousdistribution of the carbon in the oligomer can be achieved.

The carbon sources used may also be halogenated hydrocarbons of thegeneric formula C_(n)H_(2n+2−y)X_(y) where 1≦n≦5, 1≦y≦12 and X=F, Cl,Br, I. Further preferably, halogenated compounds of the generic formulaCH_(4−y)X_(y) where X=F, Cl, Br, I and y=1-3 are used. Particularpreference is given to using bromoform, dibromomethane, bromomethane,chloroform and dichloromethane.

The carbon sources used may also be carbenes of the generic formula CRR'where R, R′=—H, —F, —Br, —I, —C₁—C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,—C₂-C₁₀-(cyclo)heteroalkenyl, —C₅-C₁₀-heteroaryl, -C₇-C₁₄-aralkyl, —OR″(where R″=—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl),—NR′″₂ (where R′″=—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,—C₆-C₁₀-aryl), —Si_(n)R^(IV) _(n+1) (where R^(IV)=—H,—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl), —(CO)-R^(v)(where R^(v)=—H, —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl,—C₆-C₁₀-aryl), —(CO)—OR^(vi) (where R^(vi)=—H, —C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl), —CN, —NC, —SR^(vii) (whereR^(vii)=—H, —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl),—S(O)₂R^(viii) (where R^(viii)=—H, —C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl), —P(R^(ix))₂ (where R^(ix)=—H,—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl). It is alsopossible to use carbenes of the generic formula CRR′ in which R and R′together are a bidentate bridging radical selected from=C₃-C₂₀-(cyclo)alkyl, =C₃-C₂₀-(cyclo)alkenyl,=C₃-C₂₀-(cyclo)heteroalkyl, =C₃-C₂₀-(cyclo)heteroalkenyl or=C₆-C₁₄-(hetero)aralkyl. All alkyl, alkenyl, heteroalkyl andheteroalkenyl radicals may be linear or else branched. In addition, allalkyl, alkenyl, aryl, heteroalkyl, heteroalkenyl, heteroaryl and aralkylradicals at individual, several or all positions (more particularly oncarbon atoms and nitrogen atoms) may bear substituents. Moreparticularly, individual, several or all of these positions may behalogenated or substituted by C₃-C₆-alkyl radicals. Particularly goodresults can be achieved with carbenes of the generic formula CRR′ inwhich R and R′=—C₄-C₁₀-(cyclo)alkyl, —C₄-C₁₀-(cyclo)alkenyl,—C₄-C₁₀-aryl, -C₄-C₁₀-(cyclo)heteroalkyl, —C₄-C₁₀-heteroalkenyl,—C₅-C₁₀-heteroaryl, —C₇-C₁₄-aralkyl, or in which R and R′ together are abidentate bridging radical selected from =C₄-C₁₀-(cyclo)alkyl,=C₄-C₁₀-(cyclo)alkenyl, =C₄-C₁₀-(cyclo)heteroalkyl,=C₄-C₁₀-(cyclo)heteroalkenyl or =C₆-C₁₀-(hetero)aralkyl.

The carbon sources used may likewise be alkyl azides of the genericformula N₃R^(x) where R^(x)=—C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,—C₂-C₁₀-(cyclo)heteroalkenyl, —C₅-C₁₀-heteroaryl, -C₇-C₁₄-aralkyl, thecompounds diazomethane H₂CN₂, dimethyl sulphate C₂H₆O₄S, and alcohols ofthe generic formula HOR^(xi) where R^(xi)=—C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,—C₂-C₁₀-(cyclo)heteroalkenyl, —C₅-C₁₀-heteroaryl, -C₇-C₁₄-aralkyl.

Advantages which can result for carbon sources mentioned over othercarbon sources mentioned are that they lead particularly efficiently(i.e. particularly rapidly, in particularly high yield) to particularlyhomogeneous products. Some carbon sources may also be of particularlygood suitability compared to other carbon sources from the same compoundclass for the reaction to be catalysed.

The process according to the invention can additionally be performedparticularly efficiently when the hydridosilane has the generic formulaSi_(n)H_(2n+2) where n=3-10. Further preferably, the catalyst- andreducting agent-free reaction with the at least one carbon source iseffected in the presence of at least one further hydridosilane compoundhaving a weight-average molecular weight of at least 500 g/mol.

Particularly good boron- or phosphorus-doped hydridosilanes can beprepared from hydridosilanes of the generic formula Si_(n)H_(2n+2) wheren=3-10, a carbon source and at least one dopant selected from AlMe₃,AlCl₃, BCl₃, BF₃, diborane (B₂H₆), BH₃:THF, BEt₃, BMe₃, PH₃ and P₄.Dopants usable with particular preference are B₂H₆, BH₃:THF and P₄,which lead to particularly good doping and which additionally have theadvantage of increasing electrical dark conductivity. Because they areformed from three reactants, these oligomers are particularlyhomogeneous in relation to the distribution of the silicon, carbon anddopant atoms thereof, and as a result lead to particularly homogeneouslayers with particularly good electrical properties.

The carbon source preferably has a weight-average molecular weight of300 to 4000 g/mol (measured in cyclooctane against polybutadiene). Theseweight-average molecular weights of the carbon source particularlyefficiently avoid unilateral silicon or carbon loss in the course ofoligomerization and conversion.

The process according to the invention can likewise be performed in thepresence of a Lewis acid. Preferably, however, no Lewis acid is present.

Preference is given to performing the conversion to thecarbon-containing hydridosilane oligomer thermally and/or withelectromagnetic radiation (especially IR, VIS or UV radiation). In thecase of a thermal treatment, the reaction mixture is preferably heatedto a temperature of 30 to 235° C. These temperatures can be establishedby means known to those skilled in the art. UV irradiation isadditionally understood to mean irradiating with electromagneticradiation having wavelengths of 120 to 380 nm. VIS radiation isunderstood to mean irradiating with electromagnetic radiation havingwavelengths of 380 to 750 nm. IR irradiation, finally, is understood tomean irradiating with electromagnetic radiation having wavelengths of750 nm to 1 mm. Corresponding radiation can be generated by means knownto those skilled in the art. Preference is given to performing theconversion to the oligomer thermally or with UV radiation. Preferredreaction times are additionally between 0.1 and 12 h.

The reaction can be effected in the presence or absence of a solvent.Preference is given to performing the process according to the inventionwithout solvent. If it is performed in the presence of a solvent, thepreferred solvents used may be solvents selected from the groupconsisting of linear, branched or cyclic, saturated, unsaturated oraromatic hydrocarbons having one to 12 carbon atoms (optionallypartially or fully halogenated), ethers, ketones and esters. Particularpreference is given to n-pentane, n-hexane, n-heptane, n-octane,n-decane, dodecane, cyclohexane, cyclooctane, cyclodecane,dicyclopentane, benzene, toluene, m-xylene, p-xylene, mesitylene,tetrahydronaphthalene, decahydronaphthalene, diethyl ether, dipropylether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether,diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether,tetrahydrofuran, acetone, p-dioxane, acetonitrile, dimethylformamide,dimethyl sulphoxide, dichloromethane and chloroform. Solvents ofparticularly good usability are the hydrocarbons n-pentane, n-hexane,n-octane, n-decane, dodecane, cyclohexane, cyclooctane, cyclodecane,benzene, toluene, m-xylene, p-xylene, mesitylene. The solvent mayaccount for 0.01 to 99% by weight of the total mass.

The present invention further provides the carbon-containinghydridosilane oligomer preparable by the process according to theinvention.

The invention further provides for the use of the hydridosilaneoligomers preparable by the process according to the invention forproduction of electronic or optoelectronic component layers, especiallyfor photovoltaic applications or in transistors.

The invention likewise provides for the use of the hydridosilanespreparable by the process according to the invention for production ofsilicon-containing layers, preferably of elemental silicon layers.

The examples which follow are intended to provide further additionalillustration of the subject-matter of the invention, without themselveshaving any limiting effect.

EXAMPLES

Synthesis of the higher carbon-containing poly-H-silanes

-   -   a) Neopentasilane (1.32 g) is mixed with methylisotetrasilane        (1.18 g) and borane-THF complex (1.9 g; 1 M). The reaction        solution is stirred at 50° C. for 4 h. GPC analysis shows a        weight-average molecular weight of 500 g/mol.    -   b) Neopentasilane (3 g) is mixed with bromoform (3.48 ml) and        AlCl₃ (0.145 g), and heated gradually to 100° C. In the course        of this, a sudden onset of reaction with evolution of gas can be        observed. After the reaction has abated, the solution is        refluxed at 140° C. for a further 3 h.    -   c) Neopentasilane (1 g) is mixed with        1,3-diisopropylimidazolium-2-ylidenes (0.059 g) and borane-THF        complex (1.46 g; 1 M) at room temperature. In the course of        this, a sudden onset of reaction with evolution of gas can be        observed. After the reaction has abated, the solution is coated        according to Example 3.    -   d) Neopentasilane (1 g) is mixed with butanol (0.051 g) and        borane-THF complex (1.46 g; 1 M). The reaction mixture is heated        gradually to 140° C. and stirred at 140° C. for 3 h, in the        course of which cloudiness of the solution can be observed.    -   e) Comparative synthesis: Neopentasilane (1 g) is mixed with        borane-THF complex (1.46 g; 1 M) and stirred at 30° C. for 3 h.        A GPC analysis shows a weight-average molecular weight of 580        g/mol.

Layer Production

Example 1

A glass substrate is coated at 6000 rpm with a formulation consisting ofan oligomer from synthesis a) (0.15 g), cyclooctane (0.06 g) and toluene(0.54 g). The film is cured at 500° C. for 60 s. The layer thickness is35 nm. The optical bandgap is 1.72 eV and the conductivity 1.52×10⁻⁷S/cm.

Example 2

A glass substrate is coated at 3000 rpm with a formulation consisting ofan oligomer from synthesis b) (0.2 g), cyclooctane (0.06 g) and toluene(1.14 g). The film is cured at 500° C. for 60 s. The layer thickness is205 nm. The optical bandgap is 2.42 eV and the electrical conductivity2.1×10⁻¹¹ S/cm.

Example 3

A glass substrate is coated at 1000 rpm with a formulation consisting ofan oligomer from synthesis c) (0.156 g), cyclooctane (0.016 g) andtoluene (0.188 g). The film is cured at 500° C. for 60 s. The layerthickness is 101 nm. The optical bandgap is 1.74 eV and the electricalconductivity 2.1×10⁻⁸ S/cm.

Example 4

A glass substrate is coated at 1000 rpm with a formulation consisting ofan oligomer from synthesis d) (0.2 g), cyclooctane (0.039 g) and toluene(0.364 g). The film is cured at 500° C. for 60 s. The layer thickness is144 nm. The optical bandgap is 1.64 eV and the electrical conductivity3.2×10⁻⁵ S/cm.

Comparative Example

A glass substrate is coated at 6000 rpm with a formulation consisting ofan oligomer from the comparative synthesis (0.1 g), cyclooctane (0.1 g)and toluene (0.9 g). The film is cured at 500° C. for 60 s. The layerthickness is 98 nm. The optical bandgap is 1.54 eV.

The UV-VIS-NIR spectra were measured on the Varian Cary 5000 instrument.The carbon-containing silicon layers on glass (Corning Eagle XG) weremeasured in transmission between wavelength 200 nm and 1000 nm andplotted as a Tauc plot. The extrapolation of the linear region to the Xaxis gives the optical bandgap Eg.

1. Process A process for preparing carbon-containing hydridosilanes, inwhich an optionally boron- or phosphorus-doped hydridosilane is reactedwithout catalyst and reducing agent with at least one carbon sourceselected from linear or branched carbosilanes of the generic formulaSi_(b)H_(2b+2−y)R_(y) where b ≧2, 1 ≦y≦2b+2 and R=C₁-C₁₀-alkyl,C₆-C₁₀-aryl, C₇-C₁₄-aralkyl, cyclic carbosilanes of the generic formulaSi_(c)H_(2c−y)R_(y) where c≧3, 1≦y≦2c and R=C₂-C₁₀-alkyl, C₆-C₁₀-aryl,C₇-C₁₄-aralkyl, halogenated hydrocarbons of the generic formulaC_(n)H_(2n+2−y)X_(y) where 1≦n≦n 5, 1≦y ≦12 and X=F, Cl, Br, I, carbenesof the generic formula CRR′ with R, R′=—H, —F, —Br, —I,—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl,—C₁-C₁₀-(cyclo)heteroalkyl, —C₂-C₁₀-(cyclo)heteroalkenyl,—C₅-C₁₀-heteroaryl, —C₇-C₁₄-aralkyl, —OR″ where R″=—C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —₆-C₁₀-aryl, —NR′″₂ whereR′″=—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl,—Si_(n)R^(IV) _(n+1) where R^(IV)=—H, —C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —(CO)-R^(V) where R^(V)=—H,—C₁-C₁₀-(cyclo)alkyl, -C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl,—(CO)—OR^(vi) where R^(vi)=—H, —C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —CN, —NC, —SR^(vii) whereR^(vii)=—H, —C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl,—S(O)₂R^(viii) where R^(viii)=—H, —C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —P(R^(ix))₂ where R^(ix)=—H,—C₁-C₁₀-(cyclo)alkyl, —C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, or where Rand R′ together represent a bidentate bridging radical selected from=C₃-C₂₀-(cyclo)alkyl, =C₃-C₂₀-(cyclo)alkenyl,=C₃-C₂₀-(cyclo)heteroalkyl, =C₃-C₂₀-(cyclo)heteroalkenyl or=C₆-C₁₄-(hetero)aralkyl, —CO, CN⁻ or other carbene analogues, alkylazides of the generic formula N₃R^(x) where R^(x)=—C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀-(cyclo)alkenyl, —C₆-C₁₀-aryl, —C₁-C₁₀-(cyclo)heteroalkyl,—C₂-C₁₀-(cyclo)heteroalkenyl, C₅-C₁₀-heteroaryl, —C₇-C₁₄-aralkyl,diazomethane H₂CN₂, dimethyl sulphate C₂H₆O₄S, or alcohols of thegeneric formula HOR^(xi), where R^(xi)=—C₁-C₁₀-(cyclo)alkyl,—C₂-C₁₀(cyclo)alkenyl, —C₆-C₁₀-aryl, -C₁-C₁₀-(cyclo)heteroalkyl,—C₂-C₁₀(cyclo)heteroalkenyl, —C₅-C₁₀-heteroaryl, or -C₇-C₁₄-aralkyl. 2.The process according to claim 1, wherein the hydridosilane used as thereactant has the generic formula Si_(n){BH}_(x){PH}_(y)H_(2n+2) wheren=3-10, x=0 or 1 and y=0 or 1, with the proviso that at least one of theparameters x and y=0.
 3. The process according to claim 2, wherein thehydridosilane used as the reactant has the generic formulaSi_(n)H_(2n+2) where n=3-10.
 4. Process The process according to claim3, wherein the reaction with the at least one carbon source is effectedin the presence of at least one further hydridosilane compound having aweight-average molecular weight of at least 500 g/mol.
 5. The processaccording to claim 3, wherein the reaction of the hydridosilane with thecarbon source is effected in the presence of at least one dopantselected from the group consisting of AlMe₃, AlCl₃, BCl₃, BF₃, B₂H₆,BH₃:THF, BEt₃, BMe₃, PH₃ and P₄.
 6. The process according to claim 1,wherein the carbon source has a weight-average molecular weight of 300to 4000 g/mol.
 7. The process according to claim 1, wherein the reactionis effected thermally and/or with electromagnetic irradiation.
 8. Acarbon-containing hydridosilane oligomer preparable by a processaccording to claim
 1. 9. A method for producing an electronic oroptoelectronic component layer(s) comprising forming said layer(s) froma composition comprising a hydridosilane oligomer produced according tothe process of claim
 1. 10. A photovoltaic, transitor or otherelectronic or optoelectronic component layer(s) produced by the methodaccording to claim
 9. 11. A method for producing a silicon-containinglayer(s) comprising forming layer(s) from a composition comprising acarbon-containing hydridosilane oligomer preparable according toclaim
 1. 12. Silicon-containing layer(s) produced by the methodaccording to claim
 11. 13. Elemental silicon-containing layer(s)produced by the method according to claim 11.